N-(lower alkyl sulfonyl-methyl sulfonyl)-piperazines

ABSTRACT

This application is directed to compounds of the formula ##EQU1## wherein R 1  is lower alkyl; R 2  is hydrogen, lower alkyl or ##EQU2## wherein m is a whole number 2 to 5, n is a whole number 1 to 4 and Y is hydrogen, --OH or --COOR wherein R is hydrogen or lower alkyl; and X is ##EQU3## wherein R 3  is hydrogen or ##EQU4## wherein n and Y have the same meaning given above, R 4  is ##EQU5## wherein n and Y have the same meaning given above and R 5  is lower alkyl. These compounds are useful as silver halide solvents in photography.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to novel chemical compounds useful as silverhalide solvents in photography.

2. Description of the Prior Art

Photographic processing compositions capable of forming water-solublecomplex silver salts are known to be useful in many types of silverhalide photography. To obtain a relatively stable image in an exposedand developed photosensitive silver halide emulsion, the silver halideremaining in the unexposed and undeveloped areas of the emulsion shouldbe converted to a soluble silver complex that can be removed by washingor converted to a stable silver complex that will not "print-out" uponprolonged exposure to light. In conventional or "tray" development, itis customary to fix the developed silver halide emulsion by applying asolution of silver halide solvent, i.e., silver halide complexing agentwhich forms a water-soluble silver complex with the residual silverhalide. The water-soluble silver complex thus formed and excess silverhalide solvent are then removed from the developed and fixed emulsion bywashing with water.

Silver halide solvents also have been employed in monobaths where asingle processing composition containing a silver halide developingagent in additon to the silver halide solvent is utilized for bothdeveloping and fixing an exposed photosensitive silver halide layer.Silver halide solvents also have been employed in diffusion transferphotographic processes. Such processes are now well known in the art;see for example, U.S. Pat. Nos. 2,543,181; 2,647,056; 2,983,606; etc. Inprocesses of this type, an exposed silver halide emulsion is treatedwith a processing composition whereby the exposed silver halide emulsionis developed and an imagewise distribution of diffusible image-formingcomponents is formed in the unexposed and undeveloped portions of thesilver halide emulsion. This distribution of image-forming components istransferred by imbibition to an image-receiving stratum in superposedrelationship with the silver halide emulsion to provide the desiredtransfer image. In diffusion transfer processes where a silver transferimage is formed, processing is effected in the presence of a silverhalide solvent which forms a diffusible complex with the undevelopedsilver halide. The soluble silver complex thus formed diffuses to thesuperposed image-receiving layer where the transferred silver ions aredeposited as metallic silver to provide the silver transfer image. Inpreparing silver prints in this manner, the image-receiving elementpreferably includes a silver precipitating agent, for example, heavymetal sulfides and selenides as described in U.S. Pat. No. 2,698,237 ofEdwin H. Land.

Various compounds have been employed as silver halide solvents in thephotographic processes described above. One of the most commonlyemployed is sodium thiosulfate. Other silver halide solvents that havebeen used include thiocyanates, such as potassium and sodiumthiocyanate; and cyclic imides, such as barbituric acid and uracil. U.S.Pat. No. 3,769,014 discloses still another class of silver halidesolvents, namely, 1,1-bis-sulfonyl alkanes.

The present invention is concerned with novel compounds useful as silverhalide solvents in both conventional and diffusion transfer photography.

SUMMARY OF THE INVENTION

It is the primary object of the present invention to provide certainchemical compounds as set forth hereinafter.

It is a further object of the present invention to provide novelchemical compounds useful for complexing silver ion, i.e., undevelopedsilver halide in photographic processes.

Other objects of this invention will in part be obvious and will in partappear hereinafter.

The invention accordingly comprises the products and compositionspossessing the features, properties and the relation of elements whichare exemplified in the following detailed disclosure, and the scope ofthe application of which will be indicated in the claims.

For a fuller understanding of the nature and objects of the invention,reference should be had to the following detailed description.

DETAILED DESCRIPTION OF THE INVENTION

The novel compounds of this invention may be represented by the formula:##STR1## wherein R¹ is lower alkyl; R.sup. 2 is hydrogen, lower alkyl or##STR2## wherein m is a whole number 2 to 5, n is a whole number 1 to 4and Y is hydrogen, --OH or --COOR wherein R is hydrogen or lower alkyl;and X is ##STR3## wherein R³ is hydrogen or ##STR4## wherein n and Yhave the same meaning given above, R⁴ is ##STR5## wherein n and Y havethe same meaning given above and R⁵ is lower alkyl. In a preferredembodiment, R² is hydrogen or m is 2 or 3, n is 1 or 2, and R³ is In thequaternized compounds, the Y of the R⁴ substituent preferably is H andR⁴ and R⁵ preferably are the same.

As used herein, the term lower alkyl is intended to mean alkyl groupscontaining one to four carbon atoms, for example, methyl, ethyl, propyl,isopropyl, s-butyl and n-butyl.

Specific examples of compounds within the scope of the present inventionare as follows: ##STR6##

In preparing the non-quaternized compounds, the non-S-substitutedcompounds may be conveniently synthesized, for example, by reacting asulfene with the selected piperazine in accordance with the proceduredescribed by G. Opitz et al., Angew. Chem. Internat. Edit., Vol. 5(1966), p. 594-5. The compounds substituted with the -S-containingmoiety may be prepared, for example, by reacting the non-S-substitutedsulfonylsulfonamido alkanes with the chloro-substituted derivative ofthe selected R² substituent, i.e., ##STR7## The quaternized compoundsmay be synthesized by reacting the non-S-substituted or S-substitutedcompounds usually as a tertiary amine, i.e., R³ is other than hydrogenwith an alkyl halide or sulfonate.

The following examples are given to further illustrate the presentinvention and are not intended to limit the scope thereof.

EXAMPLE 1

Preparation of the compound having the formula ##STR8##

A solution of triethylamine (31 g., 300 mmoles) in 200 mils ofacetonitrile was chilled in dry ice/alcohol to about -50°C.Methanesulfonylchloride (23 g., 200 mmoles) was added dropwise to thecooled solution over 10 minutes with stirring. Stirring was continuedfor 20 minutes, and N-methylpiperazine (10 g., 100 mmoles) was addedover 10 minutes. The reaction mixture was allowed to stand for about 2days at room temperature and then stripped on a rotovac. The residue wastriturated with water and the title compound collected (15.3 g., meltingrange 195°-198°C.)

EXAMPLE 2

Preparation of the compound having the formula ##STR9##

The procedure of Example 1 was repeated using 44 g. of triethylamine in450 mils. of acetonitrile, 25 g. of 1-piperazine acetic acid ethylesterand 33.2 g. of methanesulfonylchloride. The title compound was collectedas a white solid (44.2 g., melting range 215°-216°C.).

EXAMPLE 3

Preparation of the compound having the formula ##STR10##

The procedure of Example 1 was repeated using 30.3 g. of triethylaminein 200 mls. of acetonitrile, 13 g. of N-(2-hydroxyethyl)piperazine in 10mls. of tetrahydrofuran and 23 g. of methanesulfonylchloride. The crudeproduct was collected and recrystallized from boiling ethanol yieldingabout 3 g. of the title compound (melting range 117°-119°C.).

EXAMPLE 4

Preparation of the compound having the formula ##STR11##

The compound of Example 1 (5 g., 19.4 mmoles) was dissolved inN,N-dimethylformamide by heating to 60°C. Sodium hydride (57% by weightdispersion in oil; 1 g.) was added to the solution and the mixtureheated at about 70°C. for 1.25 hours. The chloride, Cl--(CH₂)₂ S(CH₂)₂CO₂ C₂ H₅, (4.6 g., 23.3 mmoles) was then added over 15 minutes and thereaction mixture heated to 100°C. Heating at about 85°C. was continuedovernight and then the reaction mixture was heated at 105°C. for about 2hours. After cooling, the mixture was poured onto ice, and the filtratedecanted from a tacky gray solid. The remaining filtrate was stripped ona rotovac and the residue taken up in 50 mls. ethanol. A white solid(1.2 g.) was collected by filtration and the filtrate stripped to give asticky white solid (4.8 g.) which was triturated briefly with ether. Thetitle compound was separated from the white solid by chromatographyusing about 100 g. of silica gel which was eluted with chlorofrom, 2%methanol and 5 % methanol in 200 ml fractions. Fraction 6 containedabout 1.4 g. of the title compound, essentially homogeneous by NMR (>95% purity, melting range 124°-126°C.)

EXAMPLE 5

Preparation of the compound having the formula ##STR12##

The compound of Example 4 (1.2 g., 2.9 mmoles) was dissolved in 25 mls.of 6N hydrochloric acid and heated at reflux for 2.5 hours. The solutionwas allowed to stand overnight at room temperature and then stripped ona rotovac yielding the title compound as a white powder (1.1 g., meltingpoint about 100°C.)

EXAMPLE 6

Preparation of the compound having the formula ##STR13##

The procedure of Example 4 was repeated using 4.5 g. of the compound ofExample 1 in 25 mls. of N,N-dimethylformamide, 0.75 g. of 57% sodiumhydride and 1.92 g. of chloroethylmethylsulfide except that the reactionmixture after being poured over ice was adjusted to a pH of about 7 withapproximately 0.5 ml. of hydrochloric acid, filtered after the additionof Celite, and stripped to give a semisolid amber syrup which wastriturated with several portions of ether to give a solid ballessentially insoluble in ethylacetate. The solid was partitioned betweenethylacetate/water and the ethylacetate dried and stripped to give anamber liquid which crystallized on standing overnight. After trituratingwith ether, the title compound was collected (0.75 g.).

EXAMPLE 7

Preparation of the compound having the formula ##STR14##

The compound of Example 2 (2. g., 6.1 mmoles) was dissolved in 12 mls of3N hydrochloric acid by heating. Heating on a steam bath was continuedovernight and then the solution was filtered to remove insolubles andstripped on a rotovac to give the title compound as a white solid (1.7g., melting range 338°-340°C. dec.).

EXAMPLE 8

Preparation of the compound having the formula ##STR15##

The procedure of Example 4 was repeated using 7 g. of the compound ofExample 2 in 50 mls. of N,N-dimethylformamide, 0.9 g. of 57% sodiumhydride and 2.35 g. of chloroethylmethylsulfide except that the reactionmixture after being poured over ice was adjusted to a pH of about 7 withhydrochloric acid and allowed to stand for about 1 hour. The crystallineprecipitate that formed on standing was washed with water and trituratedwith ether to give 4 g. of the title compound (melting range 57°-60°C.).

EXAMPLE 9

Preparation of the compound having the formula ##STR16##

The compound of Example 8 (1.5 g.) was taken up in 20 mls. of 3Nhydrochloric acid and heated on a steam bath overnight. After theaddition of Celite, the solution was filtered and stripped on a rotovacleaving a brittle foam which upon standing for several days gave aglass. The glass was taken up in water to give a 50% aqueous solution.After standing for several days, a tan solid crystallized which wascollected to give 0.5 g. of the title compound (melting range196°-198°C. dec.).

EXAMPLE 10

Preparation of the compound having the formula ##STR17##

The compound of Example 1 (1.25 g., 4.9 mmoles) was dissolved in 25 mlsof acetonitrile by warming and the solution allowed to cool to roomtemperature. Methylfluorosulfonate (0.56 g., 4.9 mmoles) was added tothe cooled solution and the reaction mixture was warmed briefly. A whitesolid separated, and after about 15 minutes when the reaction mixturehad cooled to room temperature, the white solid was collected to give1.4 g. of the title compound.

As noted above, the compounds of the pesent invention are broadly usefulin a variety of photographic processes of the type in whichwater-soluble silver complexes are formed from the unreduced silverhalide of a photoexposed and at least partially developed silver halidestratum including both conventional and diffusion transfer photographicprocesses. The photographic use of these compounds as silver halidesolvents in photographic processes forms the subject matter of copendingU.S. Pat. application Ser. No. 564,167 of Richard B. Greenwald filedconcurrently herewith. For convenience, the specification of saidapplication is specifically incorporated herein.

To illustrate the utility of the above-defined compounds as photographicsilver halide solvents, a photo-sensitive silver halide emulsion on asupport was exposed to a step wedge and processed by spreading a layerof processing composition approximately 1.2 mils. thick between theexposed emulsion and a superposed image-receiving element comprising alayer of regenerated cellulose containing colloidal palladium sulfidecarried on a transparent support. The processing composition wasprepared by adding a compound of the present invention in aconcentration of 5% by weight to the following formulation:

    Water                814.0    g.                                              Potassium hydroxide                                                           (Aqueous 50% w/w solution)                                                                         348.0    g.                                              Hydroxyethyl cellulose                                                                             35.0     g.                                              Zinc acetate         15.0     g.                                              Triethanolamine      5.6      g.                                              Bis-N,N-methoxyethyl                                                          hydroxylamine        50.0     g.                                          

After an imbibition period of approximately one minute, the developedsilver halide emulsion was separated from the image-receiving element,and the maximum and minimum transmission densities were measured for thepositive image.

The compounds added to the base formulation as silver halide solvents,and the density measurements for the positive image obtained with eachof the compounds are set forth in the following table:

                  TABLE                                                           ______________________________________                                        Compound     Density                                                          (Formula No.)                                                                              Maximum       Minimum                                            ______________________________________                                        (2)          2.32          0.26                                               (3)          1.70          0.09                                               (4)          1.67          0.08                                               (15)         0.98          0.30                                               ______________________________________                                    

The compounds of the present invention have been found to give highermaximum densities than the corresponding compound with otherheterocyclic groups in place of the 1-piperizinyl group. For example,the foregoing procedure was repreated using ##STR18## The densitymeasurements for the positive image obtained, i.e., D_(max) /D_(min)were 0.55/0.07, 0.08/0.02 and 0.49/0.06, respectively.

Since certain changes may be made in the above composition and processeswithout departing from the scope of the invention herein involved, it isintended that all matter contained in the above description should beinterpreted as illustrative and not in a limiting sense.

What is claimed is:
 1. A compound of the formula: ##EQU6## wherein R¹ islower alkyl; R² is hydrogen or lower alkyl; ##EQU7## wherein A is ahalide of a sulfonate; wherein R³ is hydrogen or --(CH₂)_(n) --Y whereinn is a whole number 1 to 4; Y is hydrogen, --OH or --COOR wherein R ishydrogen or lower alkyl; R⁴ is --(CH₂)_(n) --Y wherein n and Y have thesame meaning given above and R⁵ is lower alkyl.
 2. A compound as definedin claim 1 wherein R² is hydrogen.
 3. A compound as defined in claim 1wherein X is ##STR19##
 4. A compound as defined in claim 1 wherein X is##STR20## wherein A is a halide or a sulfonate.
 5. A compound as definedin claim 3 wherein R³ is ##STR21##
 6. A compound as defined in claim 4wherein said Y of said R⁴ is hydrogen.
 7. The compound having theformula ##STR22##
 8. The compound having the formula ##STR23##
 9. Thecompound having the formula ##STR24##
 10. The compound having theformula ##STR25##
 11. A compound as defined in claim 3 wherein R² ishydrogen.